Triazinylaminoalkyl phosphonates

ABSTRACT

Novel triazinylaminoalkyl phosphonates, methods for their preparation as well as for their use in preparing flameproof finishes for textiles are disclosed. These triazinylaminoalkyl phosphonates are found to be low in cost and of minimal toxicity and their use for the flameproofing of textiles provides highly durable finishes.

ilmited tetes Patent [191 eil et a1.

[451 Aug. 28, 1973 TRIAZINYLAMINOALKYL PHOSPHONATES Inventors: Edward D. Weil,

Hastings-on-Hudson; Ralph Fearing, Bardonia, both of N.Y.

Stauifer Chemical Company, New York, NY.

Filed: June 26, 1970 Appl. No; 50,364

Assignee:

US. Cl 260/249.6, 260/2498, 260/2495, 252/8.1, 71/93, 117/137 Int. Cl C07d 55/22 Field of Search 260/2495, 249.8, 260/2496 [56] References Cited UNITED STATES PATENTS 3,551,422 12/1970 Tesoro et a] 260/2496 Primary Examiner-John M. Ford Attorney-Wayne C. Jaeschke, Martin Goldwasser and Rocco S. Barrese 57] ABSTRACT 5 Claims, No Drawings TRIAZINYLAMINOALKYL PHOSPI-IONATES BACKGROUND OF THE INVENTION The literature discloses numerous examples of attempts to achieve flame retardant textile finishes based on phosphorus containing triazine or melamine compounds. Early efforts in this area are exemplified by the use of co-condensates of methylol melamines with acidic phosphorus compounds as is taught in U.S. Pat. Nos. 2,582,961; 2,781,281 and 2,711,998. These textile finishes were rather inefi'icient inasmuch as they contained phosphorus which was in the form of acidic or ionic structures and which could, therefore, be leached out during laundering or which would undergo ion exchange with sodium and calcium ions in the wash water so as to render the phosphorus ineffectual for flame retardancy purposes. Such finishes are at best semi-durable, being capable of surviving, at most, only one or two launderings.

The prior art also discloses flame retardant textile finishes containing phosphoramide or phosphoramidate linkages, i.e.

linkages. Such products are described in British Pat. No. 835,581 and in U.S. Pat. No. 2,971,929. However, the durability of phosphoramide finishes is again somewhat inadequate as noted by Jones et al., J. Applied Chem. 12, (9), 397-405 (1962) and by Frick et al. in PB Report 151 550 (U.S. Govt. Research Rept. 31,340).

Another group of triazine-phosphorus flame retardants have the phosphorus attached directly to the triazine ring and are prepared by means of the Arbuzov reaction between cyanuric chlorides with alkyl phosphites. Although such compounds may be thought to possess a stable structure, it has been found that they are, in fact, readily hydrolyzable as was commented upon by Morrison, J. Org. Chem. 22,444, (1957). Thus, such textile finishes are quite deficient in their durability as noted by Frick et al. in PB Report 151 550 (U.S. Govt. Research Rept. 31,340) and in U.S. Pat. No. 3,210,350. In addition, it should be pointed out that finishes of this type must be synthesized from cyanuric chloride which is far more expensive and toxic than melamine.

Still another class of flame retardant textile finishes disclosed in the prior art are of the products resulting from the co-condensation of phosphine derivatives with methylolmelamines, e.g. the use of dibutyl phosphine as taught in U.S. Pat. No. 3,050,522 and the use of tetrakis (hydroxymethyl) phosphonium chloride or hydroxide as taught in British Pat. Nos. 882,993 and 884,785 and in U.S. Pat. Nos. 2,722,108; 2,809,941; 2,812,311 and 2,911,322.

Although the latter class of textile finishes has been more successful than those described hereinabove, they still enjoy little or no commercial usage because of several inherent deficiencies. Thus, the phosphorus in these products is brought into the system in a relatively expensive form involving the use of a toxic phosphine. Secondly, the phosphine derivatives are, in general, quite toxic and difficult to handle during the textile finishing operation wherein a careful control of pH is required. In addition, the tetrakis (hydroxymethyl) phosphonium chloride based finishes have been found to impart a generally poor hand to the resulting finished fabrics. A critique of this class of finishes may be found in Hall, Textile Recorder, Feb. 1966, pp. 64-7 and Reeves et al., Textile Chemist & Colorist 1,365. (1969).

It is, therefore, the prime object of this invention to provide a novel class of phosphorus containing melamine derivatives for use in the preparation of flame retardant textile finishes. It is a further object to provide phosphorus containing melamine derivatives characterized by their low cost and toxicity as well as by their ability to yield highly durable textile finishes which will retain their fire retardant properties after being subjected to repeated launderings. Various other objects and advantages of this invention will be apparent from a reading of the disclosure which follows hereinafter.

TECHNICAL DISCLOSURE OF THE INVENTION It has now been discovered that a novel class of relatively inexpensive and non-toxic triazinylaminoalkyl phosphonates is capable of providing durable flame retardant finishes for both natural and synthetic textiles, which retain their flame retardant properties after numerous launderings.

The triazinylaminoalkyl phosphonates of this invention may be described as those compounds corresponding to the structural formula:

where A, B, and C are selected from the group consisting of halogen and -NR R groups with at least one of A, B, and C being an -NR'R group, in which R and R are selected from the group consisting of hydrogen, C,C alkyl, C,C hydroxyalkyl, methylene, methyleneoxymethylene methylol, C -C alkoxymethyl and Z, where Z is a phosphonate radical of the structure where n is an integer having a value from 0 to 1, R and R are selected from the group consisting of hydrogen and C -C alkyl, and R and R are selected from the group consisting of alkyl, C C alkoxyalkyl, allyl, C -C 2-haloalkyl, C -C Z-hydroxyalkyl, and aryl, with the proviso that at least one Z group is present in the molecule of said triazinylaminoalkyl phosphonate and that where R and/or R is a methylene or methyleneoxymethylene group, the remaining valence thereof is attached to another triazine nucleus having substituents as here defined.

A preferred group of compounds within the above defined triazinylaminoalkyl phosphonates, in view of their case of preparation and enhanced suitability for flameproof finishing of textiles, are the melamine N- alkylphosphonic esters wherein all three radi-cals A, B, and C, as defined above, have the structure NRR where R and R are selected from the group consisting of hydrogen, methylol, C -C alkoxymethyl, methylene, methyleneoxymethylene, and 2 where Z is as defined above.

where each of A, B, and C is a group having the structure NRR wherein R and R are selected from the group consisting of hydrogen, methylol, methylene, methyleneoxymethylene, C C alkoxymethyl, and Z where Z is a phosphonate radical of the structure 0 2 l i o filkynlzv with the proviso that at least one of the R and R groups in the molecule is a Z group and that at least one of the R and R groups in the molecule is a methylol or C -C alkoxymethyl group and that no more than two of the R and R groups in the molecule is hydrogen.

The mixtures of the above defined compounds are products of the various processes described hereinbelow wherein precursor triazine compounds containing methylol groups in those positions where Z groups are desired in the final reaction product are reacted in liquid or slurry phases with a (C,C alkyl-O) P reagent until trivalent phosphorus is substantially absent from the re-action mixture. Where C -C alkoxymethyl groups, rather than methylol groups are to be conscribed hereinbelow and (2) heating in the liquid phase 55 with a (C,C alkyl-O) PHO reagent until HP- bonds are substantially undetectable in the reaction mixture 60 by the usual mercurometric or infrared analytical methods. In each of these three types of reactions for preparing these preferred mixtures of compounds, some condensation of methylol or C,-C,, alkoxymethyl groups to methylene or mcthyleneoxymethylenc 5 bridges conjoining melamine nuclei occurs to a greater or lesser degree depending on the particular conditions of time, pH and temperature, etc. which are utilized in the reaction. The products of these processes are, therefore, usually mixtures of condensed as well as mononuclear compounds as is commonly the case in the art of melamine/formaldehyde resins. As was noted above, these mixtures are particularly useful for the fiameproofing of cotton textiles and it is also to be pointed out that they are well suited for this purpose since they may be applied from either aqueous or organic solvent solutions.

This invention, therefore, comprehends the preparation and use of: 1) mixed products of a typical resinous nature, both the individual components of these mixtures and the mixtures per se being within the scope of the invention and (2) individual molecular species such as can be systematically synthesized as, for example, from cyanuric chloride by means of a process involving the stepwise replacement of the chlorine atoms by reagents containing HNRR groups wherein R and R are as defined above and which may be the same or different.

As has been noted, there are a number of preparative procedures which may be used to synthesize the novel triazinylaminoalkyl phosphonates, and the mixtures thereof, of this invention. in brief, the various processes for the preparation of these triazinylaminoalkyl phosphonates comprise reacting, at from about -200 C., at least one precursor triazine compound selected from the group consisting of polymethylol or methylolated melamines, polyalkoxymethylmelamines, cyanuric chloride, chloromethylmelamine and C,-Cl8 alkoxymethyl melamines and from about 0.3 to 6 moles, per mole of said precursor melamine compound, of at least one phosphorus containing reagent selected from the group consisting of trialkyl phosphites, phosphorus trihalides, dialkyl l-arninoalkyl phosphonates, dialkyl phosphonates and hydroxyalkyl phosphonates. The details of these various processes are described hereinbelow.

Process No. 1 The derivatives of this invention can be prepared by means of a liquid phase reaction between from about 0.3 to 6, and preferably l-5, moles of a trialkyl phosphite, such as triethyl phosphite, and one mole of a methylolmelamine or of a substituted methylolmelamine having sufficient methylol groups to react with substantially all of the trialkyl phosphite. The reaction may be conducted with pure methylolmelamines which dissolve when phosphonated or with crude methanolic reaction solutions or inert solvent suspensions such as one might directly obtain by means of known prior art procedures from melamine and formaldehyde. The reaction is conducted at temperatures in the range of from about 0 to 200 C. until all of the phosphite has reacted to form phosphonate groups as may be determined by such means as a mercurometric assay for phosphite groups, by nuclear magnetic resonance or by distillation or the evolved alkanol by-product. The reaction mixture may then be stripped, usually under vacuum, at a temperature of from about 0 to 200 C. yielding the desired triazinylaminoalkyl phosphonate as a residue which may be in the form of a syrup or gummy resin that is soluble in water and in many organic solvents such as alcohols, trichloroethylene and chloroform. The preparation of triazinylaminoalkyl phosphonates by means of this type of reaction is surprising since (1) reaction conditions, even when the the methylol melamine is insoluble in the trialkyl phosphite, are unexpectedly mild, (2) the reaction is rapidly quantitative (3) pure intermediates are not required, and (4) the pentavalent phosphonate is obtained rather than the phosphite which might be expected by mere transesterification. Process No. 2 These derivatives can be prepared by means of the reaction, in the liquid phase, between one mole of an alkoxymethylmelamine, such as hexamethoxymethylmelamine, about 0.1 to 2 moles of a phosphorus trihalide, such as phosphorus trichloride and from 0.3 to 6 moles of a trialkyl phosphite such as trimethyl phosphite. The latter reagent is first preferably added to the melamine derivative, although premixing with the phosphorus trichloride, as well as other modes of addition, are also permissible. It is believed that the conversion is a sequence of two exothermic reactions which is carried out at a temperature of from about 20 to 180 C., and preferably at 0l20 C., and for a period of from about 1 minute to 50 hours depending upon the temperature that is utilized. The first reaction in this sequence is a conversion, by PCl of the methoxymethyl groups on the resin intermediate to the form of chloromethyl groups while the second reaction in the sequence is between these chloromethyl groups and the trialkyl phosphite to produce the desired amino methylphosphonic diester groups. If the phosphorus trichloride is premixed with excess trialkyl phosphite, dialkyl phosphorochloridite is formed which can react with the resin in a manner which can be represented as a one step overall equation. In either case, the reaction mixture may be heated, after the addition of the trialkyl phosphite, until trivalent phosphorus is no longer detectable, whereupon it is stripped of the alkyl chloride by-product. Process No. 3 Triazinylaminoalkyl phosphonates can be prepared by reacting one mole of cyanuric chloride with from about 1 to 3 moles of a dialkyl l-aminoalkylphosphonate, such as diethyl l-aminoisopropylphosphonate, in the optional presence of an equivalent amount ofa base which serves as an HCl acceptor as, for example,,triethylamine, sodium carbonate, pyridine or the like. Or, the dialkyl laminophosphonate may itself serve as the acid acceptor in which case one mole out of each two moles introduced will serve in this capacity while the other will be introduced into the reaction product molecule. This reaction is conducted in the liquid phase, preferably in a solvent for cyanuric chloride, at a temperature of from about 0 to C. until the desired 1 to 3 moles of chloride ion is released. After removal of the byproduct chloride salt formed by reaction of the base with the evolved hydrogen chloride, the desired reaction product is generally isolated by evaporation of the solvent, by chilling, or by addition of a non-solvent therefor. This process is especially useful for preparing halotriazinylaminoalkylphosphonates, and specific isomers of the compounds of this invention, since the three chlorine atoms of cyanuric chloride react stepwise, the first very rapidly, the second much less rapidly, and the third quite slowly. By successive use of different reactants, having the structure 'NHR R i.e. ammonia, primary amines or secondary amines, compounds can be produced having NR'R groups, as defined above, where at least one of the R or R groups is a phosphonate group.

The synthesis of individual molecular species is straightforward by this method. Thus, two or three different NRR groups can be placed on the triazine ring. The reaction conditions for these successive steps are in themselves known for non-phosphonated amines, and are described, for example, by Gysin and Knusli, in Advances in Pest Control Research, Vol. Ill, lnterscience Publishers, Inc., NY. pp. 295-300 (1960). The preparation of the requisite HNR'R reactants where at least one of the R and R groups is a phosphonoalkyl group Z may be conducted by means of any of the methods set forth in Vol. l2/i, pp. 483-489 of Houben-Weyl, Methoden der Organisch'en Chemie.

Process No. 4 The derivatives of this invention can be prepared by first reacting one mole of an alkoxymethylmelamine with from about 0.3 to 6, preferably 1 to 5, moles of phosgene gas at a temperature of from about to 50 C. for a period of about 1 to 5 hours to obtain a chloromethylmelamine. This reaction is set forth in US. Patent No. 3,317,529. After vacuum distiiling to remove volatiles, each mole of the residue is slowly reacted with about 0.3 to 6, preferably 1 to 5, moles of a trialkyl phosphite, such as triethyl phosphite, at to 150 C.; the concentration of the latter reagent being equivalent to the number of moles of phosgene used is the prior atep. Distillation yields an alkyl chloride as a by-product leaving the desired triazinylaminoalkyl phosphonate as a residue.

Process No. 5 These derivatives can be prepared by reacting about 0.3 to 6, preferably 1 to 5, moles ofa dialkyl phosphonate, such as a dimethyl phosphonate, with one mole of an alkoxymethylmelamine, such as hexamethoxymethylmelamine or a fully or partially methylated pentamethyloimelamine at a temperature of from about 20 to 200C. for a period of from about 0.1 to 48 hrs. until substantial completion of the reaction is shown by infra-red, nuclear magnetic resonance or oxidimetric analysis for unreacted dialkyl phosphonate or by distillation of the desired quantity of byproduct alkanol. A trialkyl phosphite may also be pres ent in the system in order to scavange any acids formed by side reactions. if desired, the resulting reaction mixture may be used as is or it may first be stripped free of traces of unreacted dialkyl phosphonate and byproduct alkanol.

Process No. 6 Another synthetic route involves the reaction between one mole of an alkoxymethylmelamine, such as heamethoxymethylmelamine, and 0.3 to 6, preferably 1 to 5, moles of a trialkyl phosphite, such as trimethyl phosphite, and from about 0.3 to 6, preferably 1 to 5, moles of a proton donor which may be an organic acid, such as acetic acid, a phenol or an alcohol. This reaction is run at a temperature of from about 20 to 200 C. for a period of from about 0. l to 48 hours until substantial completion of the reaction is shown by infra-red, nuclear magnetic resonance or oxidimetric analysis for unreacted dialkyl phosphonate or by distillation of the desired quantity pf by-product alkanol. If desired, the resulting reaction mixture may be used as is or it may be stripped free of traces of unreacted trialkyl phosphite and proton donor. The alkylation product of the proton donor, such for example as alkyl acetate where acetic acid is used as the proton donor, is also formed as a by-product and may be removed by distillation.

Process No. 7 A synthetic route suitable for the preparation of the compounds of this invention where (I -C alkoxymethyl group where the group Z is to be present in the product, with from about 0.3-6 moles of a selected dialkyl l-hydroxyalkyl phosphonate having the structure 0 ll 1100mm 1* 0 run.

This reaction is preferably run at about 20-200 C. in the presence of an acid catalyst until substantially one molar equivalent of water (in the case where the precursor melamine compound contains a CH,OH group) or alcohol (in the case where the precursor melamine compound contains a CH o-alkyl group) has been evolved, as determined by means of some suitable analytical technique such as by distillation and collection of the water or alcohol.

In any of the above-described processes, where the resulting product contains -CH,Ol-l groups, it is possi ble to subsequently etherify such CH OH groups by the addition of an alcohol, preferably a primary alcohol, in the presence of an acid catalyst. Such etherification processes are, of course, well known in the melamine/formaldehyde resin art. Furthermore, in any of the above described processes, where the resulting product contains NH groups, it is possible to methylolate such NH groups so as to convert them into -N(CH OH) groups by reaction with formaldehyde in the manner well known in the melamine-formaldehyde art. Such N(CH Ol-l) groups may then be etherified in the manner described hereinabove.

In conducting the above described reaction processes of this invention, those involving the use of at least one liquid reactant can be run without the use of a diluent or solvent. However, in order to improve upon heat transfer, ease of mixing and other engineering considerations, diluents or solvents can be employed with the proviso that they are sufficiently non-reactive towards the respective reagents and reaction products. Suitable diluents include, for example, hydrocarbons, halogenated hydrocarbons such as chloroform, trichloroethylene, and the like. In some cases ketones, alcohols and water can be used provided that the reaction rate of these solvents with the trivalent phosphorus compound are slower than the desired reaction.

In the appropriate reaction procedures described hreinabove, trimethyl, triethyl, tripropyl, tributyl, trioctyl, trioctadecyl, triallyl, tris-2-chloroethyl, tris-2- chloropropyl, dimethyl ethyl, diethyl propyl, methyl diethyl and ethyl dipropyl phosphite, etc. are all applicable for use as trialkyl phosphites; dimethyl, diethyl, dipropyl, dibutyl, diallyl, bis(2-chloroethyl), dioctyl, methyl ethyl and methyl propyl phosphorochloridite, etc. are all applicable for use as dialkyl phosphorochloridites; dimethyl l-aminomethyl phosphonate, diethyl l-aminomethyl phosphonate, diethyl l-aminoethylphosphonate, dimethyl l-aminoethylephosphonate, diethyl l-ethylaminomethylphosphonate, diisopropyl 1-n-propylaminoisopropylphosphonate, tetraethyliminobis-methylphosphonate and diallyl l-methylamino'm butylphosphonate, etc. are all applicable for use as dialkyl l-aminoalkylphosphonates; dimethyl, diethyl, dipropyl, dibutyl, diallyl, bis(2-chloroethyl), dioctyl, didodecyl, dioctadecyl, methyl ethyl and methyl propyl phosphonate, etc. are all applicable for use as dialkyl phosphonates; and, dimethylolmelamine, trimethylolmelamine, tetramethylolmelamine, pentamethylolmelamine, hexamethylolmelamine, tetramethylol methylenebismelamine, tris(methoxymethyl)melamine, tetra-, pentaand hexakis(methoxymethyl)melamine, partially methylated tri-, tetra-, pentaand hexamethylolmelamine and, partially or fully ethylated tri-, tetra-, penta-, or hexamethylolmelamine are all applicable for use as alkoxymethylmelamines. Also suitable are methoxymethylated methylene (or methylene oxymethylene) bismelamine dimers and trimers, etc.

The novel triazinylaminoalltyl phosphonates of this invention may be characterized as colorless viscous liquids or syrups or as readily fusible resins all of which are at least partially soluble in water and in many of the common organic solvents such, for example, as alcohols, ketones, methylene chloride, methyl chloroform, chloroform, ethylene dichloride, trichloroethylene, xylene and perchloroethylene. At 50 C., these compounds generally hydrolyze at a rate of less than about 1 percent, by weight, per hour. They are distinguished from the phosphorus substituted melamine compounds of the prior art since they are non-ionic neither ionizing nor, as noted above, undergoing extensive hydrolysis in water under ordinary conditions of use. And, as will be noted, hereinbelow, these compounds can be cured, by acid catalysis, so as to form insoluble thermoset resins.

As has already been noted, hereinabove, the triazinylaminoalkyl phosphonates of this invention provide excellent results when utilized as flame proofing finishes for both natural and synthetic textile materials. It is also noteworthy to point out that the finishes derived from these derivatives may also be characterized as durable press finishes since they permit the textiles to which they have been applied to retain their original shape and remain wrinkle-free after being laundered without any need for having them ironed.

Textiles may be treated with the derivatives of the invention while the latter are dissolved in an aqueous mediumor, if desired, they may be applied while in the form of organic solvent solutions utilizing such essentially non-polar solvents as methylene chloride, ethylene dichloride, trichloroethene, perchloroethylene, etc. and mixtures thereof. This ability to employ the novel derivatives of this invention in organic solvent media, the use of which is becoming increasingly more important in the textile finishing art, represents a distinct advantage with respect to the flame retardant compositions of the prior art which generally lacked organic solvent solubility.

The solutions, either aqueous or organic solvent, containing one or more of the triazinylaminoalkyl phosphonate derivatives of this invention, may be applied to textiles by the use of any desired procedure. It is merely necessary to have the triazinylaminoalkyl phosphonate absorbed throughout the mass of the textile and/or to apply it to at least one surface thereof by means of any convenient procedure. Thus, they may be applied by being sprayed onto one or both surfaces of the textile or, as is more frequently the case, the textile may be passed or padded through the solution while the latter is being held in a tank or other suitable container. Such a process is commonly referred to as a padding technique with the solution being referred to as a padding bath" or padding solution.

The concentration of the triazinylaminoalkyl phosphonate within the padding bath, or other applicable solution, will be dependent upon a number of factors including the nature of the fibers which comprise the textile, the weight and weave of the textile, the degree of flameproofing that is desired in the finished textile, as well as other technical and economic considerations known and understood by those skilled in the art. However, it is generally desirable that the padding bath should contain from about 5 to percent, by weight, of one or more of the triazinylaminoalkyl phosphonate; the latter concentration being sufficient to deposit a finish upon the textile which will contain from about 5 to 75 percent, by weight of the textile, of the triazinylaminoalkyl phosphonate which, in turn, will provide the thus treated textile with about 0.2 to 7.5 percent, by weight of the textile, of phosphorus. Again, it is to be stressed that the latter limits are merely illustrative and may be varied so as to provide a textile finish having any desired degree of flame retardancy.

Subsequent to their deposition upon and/or their absorption by a textile, the triazinylaminoalkyl phosphonates contained within the padding solution may be cured, or crosslinked, so as to yield a highly durable, fire retardant finish. This curing operation may be accomplished by maintaining the treated fabric for a period of from about 1 hour to 10 days at ambient temperatures, or, a more rapid cure may be affected by the application of heat at temperatures of up to about 200 C. Under the latter conditions, a curing time as short as only about one second may be required. Additional control of the curing rate may be achieved by the optional presence in the padding solution of various adjuvants including pH controlling substances such as acid releasing salts which accelerate or catalyze the rate of cure or basic substances which will, on the other hand, retard the cure rate.

Rate retarding substances include, for example, alkali metal hydroxides, such as sodium hydroxide, and alkali metal bicarbonates and carbonates such as sodium bicarbonate and sodium carbonate. Cure accelerators, or catalysts, are exemplified by ammonium, alkaline earth and transition metal salts such as ammonium chloride, magnesium chloride, zinc chloride and zinc nitrate; amine hydrochlorides such as diethanolamine hydrochloride triethylamine hydrochloride; and, organic and inorganic acids such as acetic, oxalic, maleic, malic, citric, trichloroacetic, hydrochloric and phosphoric acids and alkyl acid phosphates. These optional curing rate retarders and accelerators may, respectively, be used alone or in combination with one another in a concentration which is sufficient to attain the cure rate desired by the practitioner. An exception to the foregoing discussion regarding catalysts and retarders comprises the compositions of this invention wherein A, B, or C are halogen. In these special cases, alkaline substances are accelerators of the desired reaction for the attachment of these special reagents to a cellulosic textile substrate while acid substances retard this reaction.

Another class of optional adjuvants which may be included within the solutions containing the triazinylaminoalkyl phosphonate derivatives of this invention, when the latter are being used for the preparation of flame retardant textile finishes, are various so called co-reactants. These co-reactants are materials which will undergo a reaction with the triazinylaminoalkyl phosphonate and which are used for various purposes such as to control the crosslink density of the finish, to improve the hand and durability of the finished textile as well as its durability, flame retardance, durable press, laundering and crease resistance properties. Particularly useful as co-reactants are aminoplast forming reagents such, for example, as urea; condensation products of urea-formaldehyde, urea-glyoxal or urea-glyoxal-formaldehyde; melamine; melamineformaldehyde condensation products; N-methylolated O-alkyl carbamates; ammonia, and formaldehyde. Each of the above described co-reactants are capable of use either alone or admixed with one another. It is to be understood, that the use, in the above given list, of the term urea is meant to include within its scope various cyclic ureas such, for example, as ethyleneurea, propyleneurea, uron, triazones, glyoxaldiurein and isocyanuric acid.

Other suitable co-reactants include forrnamide, acetamide, propionamide, dialkoxyphosphonopropionamide or the N-methylol derivatives thereof, tetrakis(- hydroxymethyl) phosphonium chloride or hydroxide, trimethylolphosphine, aminated phosphonitrilic chloride, phosphoric triamide and thermal condensation products thereof, ammonium phosphates, glycols such as the phosphorus-containing glycols and the hydroxyalkyl esters of all phosphorus acids. Particularly useful as coreactants are the novel ureidoalkylphosphonates disclosed in copending application Ser. No. 50,304 filed June 26, 1970.

In general, the triazinylaminoalkyl phosphonate finishing reagents of this invention can be made to condense during the above described curing process with co-reactant compounds having either Ol-I, -NH, -NCH OH or N-Cl-l OCI-I groups and the proper and oil-repellents such as polyfluoroalkyl compounds, silicones, acrylic acid copolymers, and the like; abrasion resistance agents such as polyacrylates, polyurethanes, and the like; colorants and color-modifying agents such as dyes, pigments, bleaches, anti-fading agents, ultraviolet screening agents and the like; antistatic agents such as quaternary ammonium compounds; humectants; bonding agents; antimicrobial agents which will supplement the inherent rotresistance and antimicrobial action of the triazinylaminoalkyl phosphonate containing finishes of this invention; and, pH modifying agents. The padding bath may also contain adjuvants intended to directly facilitate the padding operation per se, such as emulsifying and wetting agents, swelling agents, and buffers.

All types of textiles may be treated by means of the process of this invention so as to provide them with durable, fire retardant finishes. Thus, one may treat textiles derived from natural fibers such as cotton, wool, silk, sisal, jute, hemp and linen and from synthetic fibers including nylon and other polyamides; polyolefins such as polypropylene; polyesters such as polyethylene terephthalate; cellulosics such as rayon, cellulose acetate and triacetate; fiber glass; acrylics and modacrylics, i.e. fibers based on acrylonitrile copolymers; saran fibers, i.e. fibers based on vinylidene chloride copolymers; nytril fibers, i.e. fibers based on vinylidene dinitrile copolymers; rubber based fibers; spandex fibers, i.e. fibers based on a segmented polyurethane; vinal fibers, i.e. fibers based on vinyl alcohol copolymers; vinyon fibers, i.e. fibers based on vinyl chloride copolymers; and, metallic fibers. Textiles derived from blends of any of the above listed natural and/or synthetic fibers may also be treated by means of the process of this selection of such co-reactants in order to achieve a deinvention sired modification of crosslink density, crease resistance, durable press, and flame retardant properties will be evident to those skilled in the art. Some specific co-reactants which may be named are: dimethylolmela- As used in this disclosure, the term textile or textiles is meant to encompass woven or knitted fabrics as well as non-woven fabrics which consist of continuous or discontinuous fibers bonded so as to form a fabmifle; Uimelhylolmelamine; dimethylol y y ric by mechanical entanglement, thermal interfiber thyleneurea; trismethoxymethylmelamine; dimethyloluron; dimethylolethyleneurea; dimethylolpropyleneurea; N,N-dimethylol methyl carbamate; N,N-dimethylolethylcarbamate, N,N-dimethylol 2-hydroxyethylcarbamate; N,N-dimethylol methoxyethylcarbamate; urea methylolurea; dimethylolurea;

partially methylated pentamethylolmelamine; tetramethylolglyoxaldiurein; N-methylol-2- (dimethoxyphosphono )propionamide; and N- methylolacrylamide.

Various other classes of optional adjuvants may also be present in the textile finishing solutions of this invention. Thus, the padding bath containing the triazinylaminoalkyl phosphonates of this invention, and the textile finishes derived therefrom, may contain other ingredients in order to modify the finish in accordance with practices known to those skilled in the art of textile finishings.

bonding or by use of adhesive or bonding substances. Such non-woven fabrics may contain a certain percentage of wood pulp as well as conventional textile fibers in which case part of the bonding process is achieved by means of hydrogen bonding between the cellulosic pulp fibers. In non-woven fabrics, the finishing agents of this invention can serve not only as flame retardant finishes but can also contribute to .the interfiber bonding mechanism by serving as all or part of the adhesive or bonding resin component. This dual role can also be played by the finishing agents of'this invention in fabric laminates where the finishing agent can at the same time serve as the interlaminar bonding agent and as the flame retardant. In both of these systems, i.e. nonwoven fabrics and laminated fabrics, the finishing agents of this invention can also be blended with the usual bonding agents such, for example, as acrylic emulsion polymers, vinyl acetate, homoand copolymer emulsions, styrene-butadiene rubber emulsions, urethane resin emulsions, polyvinylchloride emulsions, polyvinylchloride acrylate emulsions, polyacrylates modified by vinylcarboxylic acid comonomers and the like.

In addition to being used for the preparation of fire retardant textile finishes, the novel triazinylaminoalkyl phosphonates of the invention may also be used in various other applications in which their flame retarding properties are advantageous. These include their being cured into thermoset resins which may be employed for the preparation of molded objects and coatings or for laminating or impregnating paper or wood. When used in molding resins, the novel compositions of this invention may be compounded with other thermosetting resins as well as with various tillers such as wood flours, clays, mica and the like. The uncured or thermoset resins of this invention may also be used as flame retardant additives for other resins. For example, they may be employed to crosslink hydroxyl containing polymers such, for example, as alkyds and curable acrylic polymers so as to form coatings and laminates.

In addition, certain of these triazinylaminoalkyl phosphonates display useful biological properties which include, for example, their ability to function as preemergence herbicides especially in those compounds of this invention where A and/or B is halogen. 1n the latter use, these compounds need merely be applied to the locus of the weeds, i.e. the soil, the weeds per se or to the water in the case of aquatic weeds, in a phytotoxic concentration such, for example as from 0.5 to 50 pounds per acre depending upon the weed species, soil type, duration of control required and similar factors.

The following examples further illustrate the embodiment of this invention. In these examples all parts given are by weight unless otherwise noted.

EXAMPLE I This example illustrates the preparation of one of the novel triazinylaminoalkyl phosphonates of this invention by means of reaction process No. 1 as described hereinabove.

A commercially available trimethylolmelamine (43.2 g.) and 100 g. of triethyl phosphite were stirred and heated slowly up to 153 C. until ethanol ceased to evolve (6 hours) whereupon the reaction mixture was stripped under vacuum at 150 C. to leave 91.2 g. of syrupy residue which set to a colorless water soluble solid, mp. 95-110. The product had a reasonable proton n.m.r. spectrum, i.r. spectrum, and analysis (calc. P 13.6, N 18.4; found P 13.7, N 18.8) for Comparable triazinylaminoalkyl phosphonate derivatives were obtained by the reaction, under the above described conditions, of trimethylolmelamine with trimethyl phosphite.

EXAMPLE II This example illustrates the use of one of the novel triazinylaminoalkyl phosphonate derivatives of this invention as a therrnoset coating and as part of an epoxy resin system.

Part A An aqueous solution containing 20 parts of water, 10 parts of the derivative whose preparation is described in Example 1, hereinabove, and 0.2 parts of zinc nitrate was allowed to dry on the surface of a wooden board and was then heated for 12 hours at 95 C. the resultant cured coating was hard, infusible, clear, and completely resisted attach by water or aqueous sodium carbonate. When exposed to flame, this coating intumesced yielding a foamy char which affords fire protection to the underlying flammable substrate.

Parts B A mixture of 2.8 parts of the triazinylaminoalkyl phosphonate derivative whose preparation was described in Example 1, hereinabove, and 3.4 parts of Epon 828" (a commercial epoxy resin solid by the Shell Chemical Company which is mainly the diglycidyl ether of bis-phenol A) was heated to C. and stirred to obtain a clear melt which has degassed under vacuum and then allowed to cure over 10 hrs. at 95 C. The cooled resin was clear, had a Barcol hardness of 37, and was self-extinguishing when ignited by means of a Bunsen burner.

EXAMPLE [B This example illustrates the preparation of another of the novel triazinylaminoalkyl phosphonates of this invention; the procedure utilized in this case being reaction process No. 2 as described hereinabove.

Phosphorus trichloride (27.5 grams, 0.2 mole) was mixed with 200 grams of trimethyl phosphite and maintained at 150-40 C. for three hours so as to obtain redistribution to a mixture estimated as containing up to 0.6 mole of dimethyl phosphorochloridite and 1.2 moles of excess trimethyl phosphite. This was then slowly added at 50 C. to 156 grams of hexamethoxymethylmelarnine (0.4 moles). The exothermic reaction period was followed by an additional 1% hours of heating (6575 C).

Successive stripping at 250 mm., mm., and 0.1 mm., yielded the expected methyl chloride (BF-22) and excess trimethyl phosphite. The desired reaction product weighed 200 grams. Analysis calculated for 1% phosphonate groups per mole:

Total P, 9.1; P', nil.

Found P, 8.0; P, 0.64.

By means of column chromatography on silica gel, monoand diphosphonate fractions may be separated and isolated. However, the crude mixture is suitable for use in many applications such, for example, as the below described textile treatment process.

EXAMPLE IV This example illustrates the use of one of the novel triazinylaminoalkyl phosphonate derivatives in the preparation of a durable, flame retardant textile finish.

The following formulation was prepared:

33 grams of the methoxymethylmelamine phosphonate ester whose preparation was described in Example lll hereinabove.

6 grams urea 8 grams of a 25%, by weight, aqueous solution of zinc nitrate 12 ml. of a 5% aqueous solution of octylphenoxypolyethoxyethanol (nonionic surfactant) This solution was brought to a pH of 6 by the addition of aqueous ammonia and was then padded onto 8 oz. cotton squares to a 75-97 percent wet pickup, dried and cured at 161 C. for 4.5 minutes. The add on of the phosphonate, after warm water rinsing, was found to be in the range of 21 to 32 percent of the total weight of the treated textile. The concentration of phosphorus found in the cloth samples was 1.08 to 1.3 percent of the total weight of the treated textile.

Flame retardancy was evaluated by the St. Hilaire semicircular frame test as described by P. St. l-lilaire,

K. Krroettner and L. E. Rossiter in Proc. A.A.T.C.C. (Nov. 18, 1968), p. 61. In this test, each of the curved or semi-circular mounted textile samples is oriented at various positions ranging from vertical to horizontal and a flame is ignited at its lower edge. If the textile is self-extinguishing in the vertical position, it is acceptable for use in all applications. If self-extinguishing when positioned at a 45 angle but not selfextinguishing in a vertical position, it is acceptable for use is less critical applications. However, if the treated textile is only self-extinguishing when in a horizontal position, the finish is only marginally acceptable and should be used only in non-critical applications. At the lowest add-on, i.e. 21 percent, the cloth did not maintain a flame, with only a 1% inch char length resulting at the near-vertical end of the curved test strip.

Moreover, after a three hour 90-95 C. treatment with a 0.5% soap -0.2% soda ash solution, the samples lost about 2 percent of weight (10 percent of the phosphonate add-on). Thereafter, in the flame retardancy test, flames were extinguished without afterglow at angles of 40-70 from the vertical.

EXAMPLE V This example illustrates the preparation of two more the hydrochloride of diethyl l-aminoisopropylphosphonate. The filtrate was evaporated and the gummy residue triturated with water to remove more hydrochloride. The residual material was taken up in ether and chilled to obtain successive crops comprising two compounds. The less soluble was a colorless crystalline solid, m.p. l52-l52.5 C. having the correct analysis (Cl calcd. 21.6, C1 found 21.7) for N N l NJ NHC(CH Reaction of this product with ethylamine affords the corresponding phosphonate which is an effective pre-emergence herbicide.

The more soluble compound derived from the residual material was a colorless crystalline solid, m.p.

128C. having the correct analysis (Cl calcd. 7.5, CI 55 found 7.5) for p s nqcnmr" (OCzHOz N N O L J-xnqcmn-w can):

When applied to weed-infested soil pre-emergence at 20 lbs/acre, this compound substantially prevented the 65 growth of annual grassy weeds.

In a similar manner, cyanuric chloride is reacted with ethylamine and then with diethyl l-aminoethylphosethylaminochlorotriazinylisopropyl phonate in order to obtain 2-chloro-4-ethylamino-6-( l- [diethoxyphosphino]ethylamino) -5-triazine which also functions as a pre-emergence herbicide.

EXAMPLE VI This example illustrates the preparation of another of the novel triazinylaminoalkyl phosphonate derivatives of this invention, the procedure utilized in this case being reaction process No. 4 as described hereinabove.

A total of 26 grams of hexamethoxymethylmelamine was treated with a slow stream of 20 grams of phosgene gas at room temperature over a period of 2% hours.

Vacuum stripping removed the methyl chloroformate byproduct. To the remaining residue, there was slowly added 0.2 moles of triethyl phosphite (34 grams in tetrahydrofuran).

Stripping at C. removed the ethyl chloride and about 14 percent of the original triethyl phosphite. Product analyses, of the residue remaining after stripping at l00C/0.0lmm. yielded 42 grams, of a product containing about 2-1/2 phosphonate ester groups per mole.

Ir Calculated for C N5(CI'IzOCII.1)aL.((Jll W0 ()zllsizlr- Found Total P 13.1% 'Irlvalent P III Nll U. 03%

By means of column chromatography, it is possible to separate the difrom the triphosphonated isomers from the latter product.

EXAMPLE VII This example again illustrates the use of another of the novel triazinylaminoalkyl phosphonates of this invention in the finishing of textiles.

A total of 3.75 grams of the triazinylaminoalkyl phosphonate derivative whose preparation was described in Example VI, hereinabove, was mixed with 0.7 g. urea; a nonionic wetting agent comprising 0.75 grams of a 5 aqueous solution of octylphenoxypolyethoxyethanol; and, 0.75 grams of a zinc nitrate catalyst. The resulting formulation was then diluted to 10 grams by the addition of water. The preparation of the latter formulation was then repeated with the addition, in this instance, of 1.0 grams of a co-reactant comprising a 50 percent aqueous solution of a partially methylated polymethylolmelamine and a dimethylolated ethyleneurea.

One gram strips of 8 oz/yd. cotton twill fabric were soaked in each of the resulting solutions, wrung to a uniform addon and dried. The following table reveals that the losses of phosphorus during curing and hot rinsing, such losses being evident when the melamine phosphonates made by means of reaction process No. 2 (see Examples III and IV) are used as finishing agents, are considerably reduced with the phosphates resulting from the use of reaction process No. 4.

Relative Loss of Phosphorus as a Percentage of the Original Phosphorus Add-On METHOD OF PREPARATION OF ADDITIVE COMPOUND Process of example Process of Proms of 6 plus the girample example coreactant Loss on drying curing at C. 8.5% of 2% of 28% of orig. P

orig. P orig. P

Los in a 55 C.

water rinse 18% of 7% of -6% of orig. P

orig. P orig. P

Lo in a soap-soda ash boil 14% of 15% of 12% of orig. P

orig. P ori P LO1= Limiting oxygen lndex as determined by the procedure described by Fenimore and Martin in the November, 1966, issue of Medern Plastics.

In brief, this procedure directly relates flame retardancy to a measurement of the minimum percentage concentration of oxygen in a oxygenznitrogen mixture which pennits the sample to burn the LOI being calculated as follows:

Thus, a higher L01 is indicative of a higher degree of flame retardancy.

EXAMPLE VlIl This example illustrates the preparation, on a large scale, of a triazinylaminoalkyl phosphonate by the use of reaction process No. 2.

A total of 625 grams of hexamethoxymethylmelamine (1.6 moles) was dissolved in 372 grams of trimethyl phosphite (3.0 moles) and treated dropwise, at 2832 C., with 110 grams of PCI;, (0.8 mole, 2.4 equivalents of chlorine) diluted with 100 grams of toluene. After the 3 hour addition period, the mixture was left standing overnight. Distillation at appropriate pressures yielded at least 80 grams of methyl chloride and 176 grams of trimethyl phosphite (plus toluene contamination). The yield of product at 70C./0.l mm. was 840 grams. These data indicate a level of phosphonation of approximately the theoretical 1% phosphonate groups per mole of triazine. To illustrate the usefulness of the thus prepared composition, a padding solution was prepared containing:

products The hand of this treated fabric was more pleasing than that of the previously prepared sample. The 1.01 of 28.1, observed after cure, was reduced only to 27.8 after the hot water rinse and five detergent washes as described above thus indicating good retention and durability on the part of this additive.

EXAMPLE IX This example illustrates the preparation of a 10 triazinylaminoalkyl phosphonate by means of reaction process No. 5 as described hereinabove.

A mixture of 330 g. (3 moles) of dimethyl phosphonate and 390 g. 1 mole) of hexamethoxymethylmelamine was heated at l-l60 C. over a period of 5 15 hours while allowing 88 g. of distillate, primarily methanol, to distill off at a vapor temperature which did not exceed the boiling point of methanol. The residual reaction mixture was then stripped free of unreacted dimethyl phosphonate and about 45 g. of volatile byleaving the desired phosphonated triazinylaminoalkyl reaction product as a colorless viscous syrup.

0 0 cm Anal. Calcd. for CJN3(CH2OCHZ1)3(CH2 1 P1609;

Found: P 14.1% (Approx. 2.6 phosphorus atoms pr-r mole Nuclear magnetic resonance showed l-"OCl-l groups (6 3.75), OCH groups (8 3.33), N--CH -O groups (6 30 5.2 and N-CH2-P groups a 4.2 No P-H signals Th b d ,bed a d y gg A portion of this solution was also heated at A 5 sl ii eofii s lnne'n ii c iy lghe ri xypolyl00-l 10 C. in order to produce a white insoluble, i.e. ethoxyethanol 0.2 thermoset, resin having flame resistant properties.

A 25%, by weight, aqueous solution of zinc nitrate 1.0

Water 68.8 X

" had 8 PH This example illustrates the preparation of a in the vertical position with a 4.75 inch char length. n

displayed a fairly good hand and no discoloration.

The thus treated cloth was then subjected to five laundry cycles, using 100 grams of detergent to 16 gallons of water (200 ppm. hardness expressed as CaCO with 10 towels, as ballast, in a Maytag washer. When dry, the cloth had an LOI of 28.0.

Another padding bath was prepared in which the concentration of the above described reaction product was reduced to 25 percent, by weight. However, it contained 5 percent, on a solids basis, of a dimethylolethyleneurea. A cured cloth which had been padded in this bath had a 16.2 percent dry add-on of this composltion.

triazinylaminoalkyl phosphonate by means of reaction process No. 6 as described hereinabove.

A mixture of 390 g. (1 mole) of hexamethoxymethylmelamine, 372 g. (3 moles) of trimethyl phosphite and 180 g. (3 moles) glacial acetic acid was heated at 98-153 C. over a 6 hour period while allowing distillate to come off at 5263 vapor temperature until 256 g. of distilled had been collected. This distillate was found to be an equimolar mixture of methanol and methylacetate. The residual reaction mixture was then vacuum stripped at 105 C. and 20mm. pressure so as to remove dissolved volatiles thereby leaving behind 631 g.

theorylorCiNa(Cl zUClia)z[Cll l o nil- .1,. $1212.,

of a viscous colorless syrup.

FOuld: 1 12.8 (about 2.4 1 atoms pmmule,

To facilitate its handling, the warm reaction product was diluted with methanol to an concentration. The resultant easily-pourable liquid was then diluted with water to a concentation of 30 percent in which form it was suitable for application to textiles.

This solution was also heated at a temperature of l1 C. so as to produce a white insoluble, thermoset resin having flame resistant properties. 5

EXAMPLE XI This example illustrates the use, in a textile finishing operation, of the triazinylaminoalkyl phosphonate whose preparation was described in Example X hereinabove.

An aqueous formulation containing the following ingredients was prepared:

% of the triazinylaminoalkyl phosphonate whose preparation is described in Example X 0.5% of a polyoxyethylated alkylphenol wetting agent 2.5% zinc nitrate Samples of 8 02. cotton twill were padded to an 88 percent wet pickup of this formulation. After drying, the samples were cured at 160 C. for 5 minutes, followed by a half hour rinsing in hot running water. After 3 hours stirring and active boiling in water containing 0.5 percent soap and 0.2 percent soda ash, the cloth samples were found to have retained 0.6 to 0.75 percent phosphorus out of the original 1.44 to 1.64 percent which was present immediately after the curing step. With another padding solution which contained 23 percent of a commercial methylolmelamine coreactant in addition to the above listed ingredients, retention was improved to two thirds of the original concentration of phosphorus which was present on the textile immediately subsequent to the cure.

EXAMPLE XII This example illustrates the preparation of a triazinylaminoalkyl phosphonate by means of a reaction process No. 5 as described hereinabove.

Two hundred sixty grams of hexamethoxymethylmelamine (0.67 moles) and 300 grams of diethyl phosphite (2.17 moles) were heated for 20 hours at 1 10 to 138 C. while under reduced pressure (80-120mm) so as to remove methanol and ethanol, the latter having resulted from transesterification with unreacted diethyl phosphite.

Stripping at a higher vacuum yielded 441 grams of a syrupy product which was found, by analysis, to have about 2.5 phosphonate groups per mole.

EXAMPLE XIII This example illustrates the use of reaction process No. 1 for the preparation of a triazinylaminoalkyl phosphonate employing, in this instance, 50 percent aqueous solution of a partially methylated polymethylolmelamine and a dimethylolated ethyleneurea as the starting reagent.

The starting reagent was stripped of its water, then 96 grams of the resulting residue was mixed with 111 grams of trimethyl phosphite (0.89 moles); the latter concentration being roughly calculated to produce a trisubstituted melamine. As the mixture was heated, it became homogeneous and, after being maintained for 4 hours at 92-120 C. and then briefly at C./200mm., about 75 percent of the theoretical methanol had distilled. The stripped residue was warmed with twice its weight of methanol at a pH of 4 whereupon it was neutralized and stripped. The latter operation converted any free N-methylo1 groups to methoxymethyl groups, thereby increasing the pourability of the product. The yield of mixed melamine N-methylphosphonic ester represented about 2.4 phosphonate groups per melamine molecule.

EXAMPLE XIV This example illustrates the use, in a textile finishing operation, of the triazinylaminoalkyl phosphonate whose preparation was described in Example XIII hereinabove.

An aqueous solution containing 30 parts of the triazinylaminoalkyl phosphonate derivative of Example XIII, 1 part of a 25 percent, by weight, zinc nitrate solution and 0.2 parts of octylphenoxypolyethoxyethanol was applied, via padding, to a 3.2 oz. per square yard cotton print cloth. The fabric was then dried at 1 10 C. for 5 minutes whereupon it was cured for 5 minutes at 163 C.

The cured fabric contained 1.6 percent, by weight, of phosphorus and produced an L.O.I. of 28. Upon subjecting the treated fabric to one detergent-free hot water wash cycle in a washing machine, the fabric was found to have retained 1.2 percent of phosphorus. The latter concentration was also retained after subjecting additional samples of this treated fabric to 5 repeated detergent wash cycles with 10 bath towels present as ballast.

EXAMPLE XV This example illustrates the preparation of a triazinylaminoalkyl phosphonate by means of reaction process No. 5 as described hereinabove.

A total of 210 grams of a polymethoxymethylmelamine which was approximately pentasubstituted with CH OCH groups was heated to l43l65C/1- 30-250mm. together with grams of dimethyl phosphite and 24 grams of trimethyl phosphite, the latter reagent being present to scavenge acidity, for a period of 6 hours so as to yield 43 grams of a slightly contaminated methanol by-product. Heating in a hot water bath, under 0.1 mm. pressure, then yielded 34 grams of unreacted dimethyl phosphite along with a residue which weighed 306 grams, thereby indicating incorporation of 1.23 phosphonate groups in the desired reaction product. Thus, about 40 percent of all of the available methoxymethyl groups were converted to methylenephosphonic ester groups.

EXAMPLE XVI This example illustrates the use for the finishing of textiles of the derivative whose preparation was described in Example XV hereinabove.

An aqueous solution containing the following ingredients was prepared:

Parts, by weight The derivative of Example XV 30.0 Zinc Nitrate (25%, by wt., aqueous solution). 1.0 Octylphenoxypolyethoxyethanol (5% aqueous solution) 0.2

Samples of 3.2 oz./yd. cotton print cloth were padded with this solution, dried 5 minutes at 110 C. and then cured for 5 minutes, at 163C, to a 26 percent add-on. The L.O.I. of the treated cloth was 26.5. After one hot water wash and five detergent washes in 16 gallons of water having a hardness of 200 ppm. CaCO using towels for ballast, the L.O.l. was 24.4.

EXAMPLE XVlI This example illustrates the preparation of a triazinylaminoalkyl phosphonate by means of reaction process No. l as described hereinabove.

A total of 150 grams of 95 percent paraformaldehyde (4.7-4.8 moles) was dissolved by heating it with 240 ml. of methanol at pH 1 1.6 to 8.8. After adding 200 ml. of additional methanol, the resulting mixture was heated, at 75C., with 126 grams of melamine (one mole) at pH 9, for 3 hours. The desire partial methylolation was achieved although the solid phase did not dissolve even after introducing an additional mole of methanolic formaldehyde. While being maintained at 4050C. 250 grams of trimethyl phosphite (2 moles) was then added dropwise over 3 hours. Analysis showed no unreacted phosphite. Gradual heating of the resulting mixture for one hour with 3 additional moles of paraformaldehyde in methanol to a temperature of 70 C. resulted in a clear solution indicating methylolation of essentially all of the unphosphonated -N-H groups particularly after an additional 20 minutes of heating at 57 C. and a pH of 8.1. With the pH lowered to 5, these hydroxymethyl groups were then methylated, at 55 C., by the large excess of methanol now present (24 moles). With the pl-i readjusted to 7, substantially all of the methanol was stripped until the resulting concentrate displayed a convenient viscosity with about 85 percent, by weight, of solids.

Variations may be made in proportions, procedures and materials without departing from the scope of this invention as defined by the following claims.

What we claim is:

1. Triazinylaminoalkyl phosphonates corresponding to the structural fonnula:

where A, B and C are NRR wherein R and R are the same or different and are selected from the group consisting of hydrogen, C C alkyl, C,C hydroxyalkyl, methylene, methyleneoxymethylene, C -C alkoxymethyl and Z where Z is a phosphonate radical of the structure myfmz it group where Z is as defined above and R is C,C, alkoxymethyl and that where R and/or R is a methylene or methyleneoxymethylene group the remaining valence thereof is attached to another triazine nucleus as here defined; and mixtures thereof.

2. The triazinylaminoalkyl phosphonates of claim 1, where R and R are the same or different and are selected from the group consisting of hydrogen, methylol, C,C alkoxymethyl, methyleneoxymethylene, and Z, wherein Z is as defined in claim 1 and R is C,-C alkoxymethyl; and mixtures thereof.

3. The triazinylaminoalkyl phosphonates of claim 2 wherein n is O, R and R are hydrogen and R and R are C -C alkyl; and mixtures thereof.

4. A process for the preparation of triazinylaminoalkyl phosphonates which comprises reacting a methylolmelamine with a trialkyl phosphite.

5. The process of claim 4 wherein, at a temperature of from about 0 to 200 C., from about 0.5 to 6 moles of a trialkyl phosphite is reacted with one mole of a methylolmelamine having sufiicient groups to react with substantially all of said trialkyl phosphite.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT N0. 3, 755,323 DATED August 23, 1973 lNV ENTOR( 1 Edward D. Weil et a1.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 22, Line 16, change "alkyl" to --al lyl--.

Signed and Scaled this Sixth D3) 0f December 1977 [SEAL] Attest:

RUTH C. MASON LUTRELLE F. PARKER Attesting Ojficer Acting Commissioner of Patents and Trademarks 5,755,325 August 28, 1975 Patent No. Dated Inventor) Edward D. Weil and Ralph Fearing It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 63, the word "radi-cals" should read radicals Column LI, line 23, the word "re-action" should read reaction Column 5, line 58, after the word distillation, the word I "or" (second occurrence) should read of Column '7', line 26, the word I'atep should read step Column 8, line 51, the word "hreinabove" should read hereinabove I Column 14, line 10, the word "has" should read was 051mm 16, line 2, the compound "[diethoxy-phosphing ethyl- 7 amino) -5-triazine" should read iethoxy phosphing ethylamino)5- triazine line ZLI,

rewrite as follows: 0 Calculated for CE73N6(CH 0on ZZCH WCI-I HQJ 0".O.-I..OOIOOQOOOIOOIOIIOO'OIC Found 3 2 line 59, after "5" add FORM PO-IOSO (10-69) USCOMM-DC 6376'P69 U.S. GOVERNMENT PRINTING OFFICE I989 0-366-334.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 5,755,323 Dated August 28, 1973 lnventm-(s) Edward D. Neil and Ralph Fearing It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 18, lines 59-60 and 62-65 should read as follows: Q I

H (theory for C N (CH OCH EH P-O-CH )g7 62A g.)

Anal. C'alcdQ for c N (cH ocH (cH f5 (o cH P 16.0 Found: I P 12.8 (about 2A P atoms per mole) Signed sealed this 20th day of August 197 (SEAL) Attest:

McCOY M. GIBSON JR. C. MARSHALL DANN Attes'ting Officer Commissioner of Patents FORM PO-IOSO (10-69) USCOMM-DC GOING-P69 0.5. GOVERNMENT rnmvms OFFICE "n o-su-su. 

2. The triazinylaminoalkyl phosphonates of claim 1, where R1 and R2 are the same or different and are selected from the group consisting of hydrogen, methylol, C1-C6 alkoxymethyl, methyleneoxymethylene, and Z, wherein Z is as defined in claim 1 and R7 is C1-C6 alkoxymethyl; and mixtures thereof.
 3. The triazinylaminoalkyl phosphonates of claim 2 wherein n is O, R3 and R4 are hydrogen and R5 and R6 are C1-C6 alkyL; and mixtures thereof.
 4. A process for the preparation of triazinylaminoalkyl phosphonates which comprises reacting a methylolmelamine with a trialkyl phosphite.
 5. The process of claim 4 wherein, at a temperature of from about 0* to 200* C., from about 0.5 to 6 moles of a trialkyl phosphite is reacted with one mole of a methylolmelamine having sufficient groups to react with substantially all of said trialkyl phosphite. 